Acid dyestuffs of the anthraquinone series



United States Patent 2,760,967 Patented Aug. 28, 1956 2,760,967 7 ACID DYESTUFFS OF THE ANTHRAQUINONE SERIES Peter Hindermann, Batterie, Basel, and Jean-Pierre'Jung, Rie hen, near Basel, Switzerland, assignors to J. R. Gelgy A. G., Basel, Switzerland, a Swiss firm No Drawing. Application July 20, 1953, Serial No. 369,227 Claims priority, application Switzerland July 31, 1952 8 Claims. (Cl. 260-374) The present invention concerns the production of new, acid dyestuffs of the anthraquinone series which are distinguished by an excellent affinity to natural and synthetic polypeptide fibres.

It has been found that new, very valuable acid'dyestuffs of the .anthraquinone series are obtained if an anthraquinone compound having two exchangeable substituents in the lX-POSltiOIlS and which can be further substituted if desired is reacted with 4-aminodiphenyl thioethers which may be further substituted non-ionogenically and the anthraquinone-bis-(p-phenylmercaptophenylamin)-compounds so obtained are sulphonated.

The new dyestuffs dye natural and synthetic polypeptide fibres such as wool, silk, lanital fibres, nylon and Perlon in very fast, particularly in very wet-fast redviolet, violet or green shades dependent on the composition of the dyestufi. They are distinguished from previously known comparable dyestuffs by their considerably improved drawing power on to wool'from a neutral bath.

Anthraquinone compounds having two exchangeable substituents in the u-position which can be used for example in the process according to the present invention are: 1.4-, 115- and .LS-dichloroor dibromo-anthralquinones, 1.5- or 1.8-dinitroanthraquinones, '1.4-, 1.5-

and 1.8-nitrochloroor nitrobromo-anthraquinones, further 1.4-dihydroxy-, diaminoor hydroxyamino-anthraquinones or the leuco compounds thereof, all of which if desired may have further non-exchangeable substit-L uents, for example halogen, in particular chlorine, in the B-position.

Amino compounds which can be used in the process according to the present invention are for example: 4- arninodiphenyl sulphide, 4-amino-2-, -2-, or -4-chlo roor -bromodiphenyl sulphide, 4-amino-2'- or -4'-methyldiphenyl sulphide, 4-amino-3.4' diniethyldiphenyl sulphide, 4-amino-4'-n-,butylor tert. amyldiphenyl sulphide, 4- amino-3'-methy1-4'-chlorodiphenyl sulphide, 4-amino-4'- methoxydiphenyl sulphide. The dyestuffs according to this invention which are derived from 4-arninodiphenyl thioethers which are substituted by halogen .or alkyl groups in the 4-positions have particularly good drawing power.

The reaction of the anthraquinone compounds usable according to the present invention with the 4-aminodiphenyl thioethers is performed by melting the components together, advantageously by the use of an excess of aminodiphenyl sulphide compound, if necessary in the presence of organic solvents or diluents. As such may be used for example high boiling alcohols and hydrocarbons or inert chlorohydrocarbons. The usual catalysts or stabilisers such as copper and compounds thereof or boric acid can be added according to the anthraquinone compounds used. If 1.4-dihydroxy, aminohydroxy, or diamino compounds are used in the condensation, it is advantageous to usea part thereof in the form of their leuco compound. This is used either as such or can be produced in the reaction mass by reduction,"

e. g. with zinc and acids. I

The 1.4-, 1.5- or 1.8-bis-(4-phenylmercapto-phenylamiuo)-anthraquinone compounds which are obtained as water insoluble dye bases are then sulphonated in sulphunc acid monohydrate, if necessary with the addition of oleum or chlorosulphonic acid and converted into the water soluble alkali salts of sulphonic acids. As such they are dark powders which dissolve well in water and they dyepolyamide fibres, particularly wool, in very wet fast and fast to-light shades even from a weakly alkaline, neutral to'weakly acid dyebath.

The following examples illustrate the invention Without limiting it in any way. Where not otherwise stated, parts are given as parts by weight and the temperatures are in degrees centigrade. The relationship of parts by weight to parts by volume is as that of kilogrammes to litres.

Example 1 75.4 parts of 4-amino-4-methyldipheny1 sulphide, 24 parts of- 1.4-dihydroxy-anth'raquinone and 8 parts of 30% hydrochloric acid are stirred at -90 and 2 parts of zinc dust are added within 20-30 minutes in small portions. After adding 5 parts of boric acid, the reaction mass is kept for 24 hours at l00-110. 200 parts of n-butyl alcohol'are then added, the whole is stirred for 30 minutes at 70?, and the condensation product which precipitates-in" crystalline form is filtered off. It is washed with 70 warm n-butyl alcohol and then made amine free by washing with greatly diluted mineral acid and finally washed with water. l.4-bis-(4'-p-tolylmercapto-anilido)-anthraquinone is obtained in an excellent yield. After drying, the base is stirred into 5-10 times the arn'ount of sulphuric acid monohydrate. The sulphonationirnass ,is-stirre d at'15-40 until a sample com pletely dissolvesjinwater. The dyestuff of the formula:

v r- CH3] SOaH which havecorresponding wet and light fastness properties.

These dye bases can also be sulphonated with chlorosulphonic acid. 10 parts of the dye base are added to a mixture of'50 parts of sulphuric acid monohydrate and 5 parts of 'chlorosulphonic acid and the whole is stirred at 10-40 until the sulphonation is complete.

Example 2 215 parts of 4-amino-4'-methyldiphenyl sulphide are heated for 10 hours at 190195 with 27.7 parts of 1.5- dichloroanthraquinone, 30 parts of potassium acetate and 0.2 part of cuprous chloride. After cooling, the melt is diluted with methanol. The condensation product precipitates in crystalline form. It is filtered off, washed with warm methyl alcohol, greatly diluted hydrochloric acid and, water and then dried. 1.5-bis-(4-p-toly1mercapto-anilido)-anthraquinone is obtained in a good yield and in a pure form.

TMOMOTHN is isolated. It is a dark powder which dissolves in Water with a violet and in concentrated sulphuric .acid with a dull yellowish brown colour. The dyestutf has excellent drawing power from a neutralbathanditdycs wool, synthetic polyamide fibres and silk in very fast red-violet shades.

If the 215 parts of 4-amino-4'nnethyldiphenyl sulphide are replaced by 201 parts of 4-.aminodiph'enyl sulphide or 257 parts of 4-amino-4nbutyldiphenyl sulphide or 271 parts of 4-amino-4-nsamyldiphenyl sulphide, violet dyestuifs are obtained, the wool dyeings .of which have similarly good washing, milling and :light fastness lproperties.

Example-3 24 parts of 1.4-dihydroxy-anthraquinone and 83 parts of 4-amino-4'-chlorodiphenyl sulphide aremelted together at 90. 8 parts of hydrochloric acid areadded and then 2 parts of zinc dust are added within 20-30 minutes in small equal portions. After adding 4.7 parts of boric acid and 10 parts of n-butyllalcohol, the whole is stirred for 24 hoursat 100-105 i. The melt at70 is .thendiluted with 150 parts of n-butyl alcohol it is stirred for 1 hour, the condensation product is drawn dfi under suction and freed from adhesive resinification' products with hot nbutyl alcohol. greatly diluted mineral'acid'anddried; The 1.4-bis-(4'- p-chlorophenylmercapto-anilido') anthraquinone formed is obtained in an excellent *yield and pure state and it can be sulphonated direct. 20 parts of'the condensation product are stirred at 2025' in 100 partsof sulphuric acid monohydrate until a sample is completely soluble in Water. The sulphonation mixture is'then poured onto a mixture of ice/sodium chloride, the 'dyestufi which precipitates is filtered ofi, neutnalised in Water'with soda and the sodium salt of the dyestufi is isolated with sodium chloride. It corresponds to theformula:

Finally it is washed free of mine with and is a dark powder which dissolves in water with a pure green-blue'shadeand in concentrated sulphuric acid with a reddish blue shade. It dyes wool, polyamide fibres, charged and uncharged silk from a neutral bath in very fast green shades.

If the .83 parts of 4-amino-4'- :hlorodiphenyl. sulphide are replaced by 98 parts of 4-,amino-4'-bromodiphenyl OKs l sulphide or 94.6 parts of -4-amino-3'.4'-dichlorodiphenyl sulphide, green dyestuifs are obtained, the dyeings with which have similarly good fastness to washing, milling and light. 1

The sulphonation can also be performed in 5-10% oleum by stirring at 15-30".

Example 4 .83 parts of 4-amino-4'-chlorodiphenyl sulphide are stirred for 5-6 hours at 165-180 with 27.7 parts of 1.4- dichloroanthraquinone, 25 parts of potassium acetate and 0.1 part of zcuprous chloride. .The condensation product precipitates in :crystalline form on the addition of 200 parts of n-butyl alcohol at .to the melt. It is filtered off and washed with warm n-butyl alcohol, greatly diluted mineralacidand Warm Water. After drying, the 1.4 -bis (4' -p -chlorophenylmercaptoanilido) anthraquinone,

which is obtained ina good yield is-stirred-in 5 to 8 times the zamount ofsulphuric acid monohydrate until a sample is .completelyso'luble in water. The-dyestufi corresponds tothatsdescribed in Example 3.

Thesamedyestuii is also obtained if, in theaboveexample, 2875 parts 'of- 1-ch1oro-4-nitro-anthraquinone or 36.6 parts'of .1.4-dibromo-anthraquinone are :used instead of 27.7 parts =of' "1.4-dichlorowanthraquinone.

Example 5 in concentrated sulphuric acid with a yellowish-brown colour.

10 parts of the condensation product :are dissolved in 6 times the amount of sulphuric acid monohydrate and the solution is stirredat25-30" until a sample is water soluble. The dyestufiof the formula:

NH W S n I HOIBI If, instead of 235.5 parts of 4-amino 4'-chlorodiphenyl sulphide, 280 parts of 4-amino-,4'-bron odiphenyl sulphide or 270 parts of 4-amino-3'.4-didhlorodiphenyl sulphide are used, a dyestuft' is obtained which dyes wool from a neutral bath in red-violet shades having similarly good wet and light fastness properties.

Example 6 215 parts of 4-amino-4'-methyldipheny l sulphide, 27.7 parts of 1.8-dichloranthraquinone, 30 parts of potassium acetate and 0.2 part of cuprous chloride are stirred at 190-195 for 12 hours. At the end of this time the-condensation is complete. The product is allowed to cool to 60, diluted with 300 parts of methanol and then boiled for 1 hour under reflux. 1.S-bis-(4'-p-tolylmercapto-anilido)-anthraquinone which precipitates in crystalline form is drawn off under suction, washed with a little cold methyl alcohol and dried. It is a-dark=crystallinepowder which dissolves in concentrated sulphuric acid with a. yellowish-green colour. I

parts of the condensation product are dissolved in 6 times the amountof sulphuric acid monohydrate and sulphonated by stirring for several hours at -25". The dyestutf of the formula:

Tlfn. SOiI HN which has been converted into the sodium salt and isolated in the usual way, is dried. It is a dark powder and dyes wool, silk and synthetic polyamide fibres from a neutral bath in fast violet shades which have good fastness to washing, milling and light. If in the above example, the 215 parts of 4-amino-4'-methyldiphenyl sulphide are replaced by 235.5 parts of 4-ainino'-4'-chlorodiphenyl sulphide, a violet dyestufi is obtained which has similar good washing, milling and light fastness properties.

This dye base can also be sulphonated with chlorosulphonic acid. For example 10 parts. of the dye base are added to a mixture of 50 parts of sulphuric acid monohydrate and 5 parts of chlorosulphonicacid'and the whole is stirred at 20-24 until the sulphonation is complete.

The dyesmfl is worked up in the usual on careful 60 6-chloro-1.4-dihydroxy-anthraquinone, 70.5 parts of 4- sulphonation it is also possible to add; less than 2 sulphonic acid groups; the dyestufls so obtained also have good properties. Example -7 231 parts of 4-amino-4'-methoxydiphenyl sulphide are heated for 10 hours at 180l90 with 27.7 parts of 1.8- dichloranthraquinone, parts of potassiumacetate and 0.2 part of cuprous chloride. After cooling to 50, the melt is diluted with 400 parts of methylalcohol. The condensation product precipitates in crystalline form." It is drawn oif under suction, washed with warm methyl alcohol, diluted hydrochloric acid and finally with water and dried. A good yield of 1.8-(4'-p-methoxyphenylmercapto-anilido)-anthraquinone is obtained in'a pure form in this manner. 1

and finally dried.

10 parts of the condensation product are dissolved in 8 times the amount of 5% oleum and the solution is stirred at 2030 until a sample completely dissolves in water. The dyestuflt' of the formula:

which has been isolated in the usual manner, dyes wool and silk from a neutral bath in fast, violet shades.

If instead of 27.7 parts of 1.8-dichloranthraquinone, 28.75 parts of 1-chloro-8-nitroanthraquinone or 33.2

20 parts of 1-bromo-8-nitroanthraquinone are used for the condensation, a dyestuff is obtained which dyes W001 and silk in similarly fast, violet shades.

Example 8 A melt made up from 75.4 parts of 4-amino-4-methyldiphenyl sulphide, 8.5 parts of 30% hydrochloric acid, 9.5 parts of leuco-l.4-diamino-anthraquinone, 14.5 parts of 1.4-diamino-anthraquinone and 5 parts of boric acid is 0 stirred for 24 hours at 100-110". 150 parts of n--butyl alcohol are added to the reaction mixture, the whole is stirred for a further hour at -90", the precipitate is filtered oil and purified with 70% n-butyl alcohol and then washed wtih greatly diluted mineral acid and Water The 1.4-bis-(4 -p-tolylmercapto-anilido)-anthraquinone so formed is obtained in a good yield and a pure state.

10 parts of the dyestufi base are dissolved in 5 times the amount of 5% oleum and stirred at l5-30 until a sample completely dissolves in water. The dyestuff which is isolated in the usual way corresponds to that described in Example 1.

Example 9 2 parts of zinc dust are added in small portions Within 20-30 minutes to a melt made up from 27.45 parts of aminodiphenyl sulphide, 10 parts of n-amyl alcohol and 7 parts of 30% hydrochloric acid at a temperature of After adding 4.7 parts of boric acid and 10 parts of n-amyl alcohol, the whole is boiled under reflux for 24 hours.

65 parts of n-amyl alcohol are then added to the reaction 75 sulphuric acid monohydrate and stirred at 1040' until a sample is soluble in water.

dyes wool, silk and polyamide fibres from a neutral bath in pure green shades which have good fastness to washing, milling and light.

If in the above example the 27.45 parts of 6-chloro-.4- dihydroXy-anthraquinone are replaced by 30.9 parts of 6.7-dichloro-1.4-dihydroxy-anthraquinone, a dyestufl? is obtained which dyes wool and silk in similarfast green shades.

Example 29.8 parts of 1.5-dinitroanthraquinone are stirred for hours at l80-185 with 250 parts of 4-amino-2-chloro- 4-rnethyldiphenyl sulphide. The condensation is then complete. 300 parts of methanol areadded at 60, the Whole is boiled under reflux for 1 ,hour, :the product is filtered oil and washed with warm methyl alcohol and finally with hot water. The l.5-bis-,(4'-p-toly1rnercapto- 3-chloranilido)-anthraquinone so formed is obtained in a pure form by crystallising from 'n-butyl alcohol.

10 parts of the condensation product are dissolved in 10 times the amount of sulphuric acid \m'onohydrate and the solution is stirred at -30 until a sample is completely water soluble. The dyestulf of the formula:

which has been converted into the sodium salt and isolated in the usual way, dyes wool and silk'from a neutral bath in fast red-violet shades.

The same dyestuff is obtained if the condensation 'is performed with 27.7 parts of 1.5-dichloranthraquinone or with 36.6 parts of 1.5-dibromanthraquinone in the presence of parts of potassium acetate and 0.3 part of copper acetate instead of 29.8 parts of 1.5-dinitroanthraquinone.

Example 11 81 parts of 4-arnino-4-methoxydipheny1 sulphide (M. P. 94-95 8 parts of leuco-l.4-dihydroXy-anthraquinone, 16 parts of 1.4-dihydroxy-anthraquinone, 4 parts of boric acid and 100 parts of n-butyl alcohol are stirred for 20-24 hours at 105l15. 100 parts of n-butyl alcohol are added to the reaction mass and, after stirring for 1 hour at 90, the precipitate is filtered off. The'filter cake is then washed with 70 warm n-butyl alcohol'and greatly diluted mineral acid until it is free of amine. By crystallising from organic solvents, the resulting 1.4-bis-'(4- p-methoxyphenylmercapto-anilido)-anthraquinone is obtained in a completely pure state.

10 parts of the dye base are-dissolved in.5 to 10 times the amount of sulphuric acid and stirred at -l540 'until 18 a sample :dissolves completely :in water. The .dyestu'fi, worked ,up in the usual way, of the formula:

dyes wool and silk from a neutral bath in fast green shades.

A dyestuff with "similar good fastness properties is obtained if 15.-8*pa 1rts'ot' =1-amino-4-hydroxy-anthraquinone are used instead of 16 parts of 1.4-dihydroxyanthra'quinone.

Example 12 83 parts of 4-amino-2-chlorodiphenyl sulphide, 24 parts of 1.4-dihydroxy-anthraquinone and 8 parts of 34% -hydrochloric *acid 'are 'stirre'cl at in a nitrogenous atmosphere and 2 "parts of 'zinc dust are added in small portions duringthestirring process. After adding 5 parts of boric acid, the melt is kept for -1'6-20 hours at *200 partsofn butyl alcohol are added, the reaction product which iprecipita'tes is filtered' ofi after stirring for -1 hour at 80-90", purified "with hot n-but-yl alcohol, greatly diluted mineral-acid and water and finally dried. The resulting *1.4-bis (4 phenylmercapto-3-chloranilido)- anthraquinone is 'otbained in a-completely pure form by crystallising from organic solvents. It is a dark crystal powder which dissolves in toluene with a green-blue and in concentrated sulphuric acid with'a reddish-blue shade.

11 0 parts ofgthe condensation product are dissolved in 50-100parts of'sulphuricacid and stirred at 15-40 until a sample completely dissolved in water.

The dyestutf,

dyes wool, polyamide fibres, charged and uncharged silk in very fastgreen shades.

- If :the 83 parts :of -4-amino+2-chlorodiphenyl sulphide are replaced :by .91 parts of 4-amino-2-ehloro-4'-methyl- .diphenyl sulphide, audyestufi is obtained which dyes W001 and silk in very'fastsgreen'shades and which has an excellent drawing :poWerefnom aneutral bath.

I Example 13 .100 parts -.of wool :flannelare-entered at 40-45 into a dyebathycontaining 1 part of the .dyestufi according to Example 3, 3 parts of ammonium sulphate or 5 parts of ammonium acetate and 10 parts of Glaubers's'alt'lin 3000 3. An :acid dyestufi of the anthraquinone series having parts of water. The bath is gradually brought to the the general formula: boil within 45 minutes, kept gently boiling for a further X r X s 30 minutes after which the dyed goods are rinsed." A is). 0 II I) 0a). very even green wool dyeing is obtained which has very good fastness to milling, sea water and light. (01),

What we claim is:

1. An acid dyestufi of the anthraquinone series having the general formula: 1 (nomlrom/ )1n 4) 0 0 wherein X1 and one of X3, X3 and X4- represent the group the others of X3, X3 and X4 each represents hydrogen, n

/ is a numeral from 0 to 2, each m may be a numeral from 2 "-0 0 n-( 3 O to 1 but the sum of the ms is at least 1 and at most 2, m

wherein X1 and one of X2, X3 and X4. represent the group being 0 in the case of said others of X2, X3 and X4, R in --NH-A1SA2, the others of X3, X3 and X4 each repthe above group representing an alkyl radical having resents hydrogen, n is a numeral from 0 to 2, each m from 1-5 carbon atoms. may be a numeral from 0 to 1 but the sum of the ms is at 4. An acid dyestufi of the anthraquinone series havleast 1 and at most 2, m being 0 in the case of said others ing the formula:

-ru owumof X2, X3 and X4, A1 in the above group representing a 5. An acid dyestuff of the anthraquinone series having p-phenylene radical and A3 representing a phenyl radical. the formula:

0 NH -01 GHQ I I -S0;H

H80 01 HN HOaB-- 2. An acid dyestuif of the anthraquinone series having the general formula:

( 15) m-(X|) 0 O-(B 0: a 45 6. An acid dyestufi of the anthraquinone series having 0 NH-iO- SUCH;}SO,H

iLmeOSOTHN ti 7. An acid dyestufl': of the anthraquinone series having the formula:

wherein X1 and one of X3, X3 and X4 represent the group -I O OH; I -SO1H the others of X2, X3 and X4 each represents hydrogen, n is a numeral from 0 to 2, each m may be a numeral 5 NH F -I from 0 to 1 but the sum of the ms is at least 1 and at lmost 2, m being 0 in the case of said others of X2, X3 and B 9013 X4, Hal in the above group representing a halogen atom.

"11 1 "8. An .acid dyestufiof the anthraquinone series having the formula: 1

.. NH-[O g;OCl-] SO3H References Cited vinthe file of this patent v I FOREIGN PATENTS 149,110. Switzerland Dec 16, 1931 597,145 I v Germany May 22, 1934 

1. AN ACID DYESTUFF OF THE ANTHRAQUINONE SERIES HAVING THE GENERAL FORMULA: 